Disazo dyestuffs metal-complex



United States Patent )flice 3,420,812 Patented Jan. 7, 1969 US. Cl.260148 7 Int. Cl. C09b 45/24; C09b 45/26; C09!) 45/28 Claims ABSTRACT OFTHE DISCLOSURE Water-soluble, disazo dyestuffs of the formula and thecomplex metal compounds of said disazo dyestuffs, wherein Ar is benzeneor naphthalene, Ar and Ar;, are benzene, naphthalene, benzene sulfonicacid, naphthalene sulfonic acid, lower alkoxy-benzene, nitrobenzene,nitrobenzene sulfonic acid, lower alkoxy-nitrobenzene sulfonic acid orchlorobenzene sulfonic acid radicals, R is hydrogen or lower alkyl, R ishydrogen or lower alkyl, R is hydrogen, hydroxyl, carboxyl or loweralkoxy, X is sulfonyl or carbonyl, Z is B-chloroethyl, fl-sulfatoethyl,fi-phosphatoethyl or vinyl, n is 1 or 2, the sum of m and m being atleast 3, and p stands for 1 or 2, and wherein the groups R in Ar and Arand OH in Ar are each linked in ortho-position to the adjacent azogroup.

The present invention relates to new water-soluble disazo dyestuffs andto their metal complex compounds as well as to a process for preparingthem; in particular,

the general formula XZ:\ I n-l m-l HO If the invention relates towater-soluble disazo dyestuffs of Rsiikrz lfi N L R Q 3 E l I N H3CC=--CO-NAr1N=NAr I L R and to the metal complex compounds thereof, i.e.,copper,

nickel, cobalt, chromium, manganese and iron complex compounds, whereinAr, represents a benzene or naphthalene radical containing at least onesulfonic acid group, Ar and Ar represent the same-or different benzene,naphthalene, benzene sulfonic acid, naphthalene sulfonic acid, loweralkoxy-benzene, nitrobenzene, benzene carboxylic acid, nitrobenzenesulfonic acid, lower alkoxy-nitrobenzene sulfonic acid and chlorobenzenesulfonic acid radicals, R represents a hydrogen atom, an aliphatic oraraliphatic radical, R represents a hydrogen atom or an alkyl group, Rrepresents a hydrogen atom, a hydroxyl, carboxyl or alkoxy group, Xrepresents a sulfonyl or carbonyl group, Z represents a fl-chloroethyl,fl-sulfatoethyl, B-phosphatoethyl or vinyl group, It stands for 1 or 2and m and m'each stand for l, 2 or 3, the sum of m+m' being at least 3,and wherein the groups R in Ar and Ar and OH in Ar are each linked inortho-position to the adjacent azo group.

Now we have found that valuable water-soluble disazo dyestuffs and themetal complex compounds thereof can be obtained by couplingsimultaneously or successively 2 mols of the same or different aromaticdiazo compounds of which at least one contains at least one group of theformula wherein R represents a hydrogen atom, an aliphatic oraraliphatic radical, X represents a sulfonyl or carbonyl group, Yrepresents a halogen atom, the radical of a polybasic acid or a hydroxylgroup, and n stands for 1 or 2, with coupling components of the generalformula B2 RlO-A.I"-l IC OCH1C 0-CH:

wherein Ar represents a benzene or naphthalene radical containing atleast one sulfonic acid group, R represents a hydrogen atom or an acylradical and R represents a hydrogen atom or an alkyl group, when usingcoupling components, in which R, designates an acyl radical, the secondmol of the diazo compound is not coupled until the acyl radical has beensplit off by saponification, whereupon in the disazo dyestuffs obtained,which contain a hydroxyl group in the groups of Formula 1, saidalcoholic hydroxyl group is esterified by treatment with polybasicacids, their monoamides or monochlorides, and, if desired, by treatingthe dyestuffs obtained with agents yielding metal, provided they containgroups forming metal complexes or capable of being converted into suchgroups.

The disazo dyestuffs obtained which contain groups of Formula 1 can beconverted, by treatment with an aqueous alkali, into disazo dyestuffscontaining groups of Formula 2. If, however, Y represents a hydroxylgroup in Formula 1, the treatment is not carried out until said hydroxylgroups has been esterified.

For the preparation of the novel disazo dyestuffs there may be used, forexample, the following diazo compo-1-hydroxy-7-acetoacetylaminonaphthalene-3-sulfonic acid,

1hydroxy-S-acetoacetylaminonaphthalene-3sulfonic acid,

1 hydroxy 8 acetoacetylaminonaphthalene 3,6 disulfonic acid,

1-hydroxy-3acetoacetylaminobenzene-4-sulfonic acid,

1 hydroxy 7 acetoacetyl N methylaminonaphthalene-3-sulfonic acid orl-(p-toluene-sulfonyloxy)7- acetoacetylaminonaphthalene-3sulfonic acid,

When operating in a weakly acid medium it is possible to couple diazocomponents having a low coupling energy, such, for example, asortho-aminophenol derivatives or ortho-aminonaphthol derivatives or2-arninobenzoic acid,

only once with the coupling components of the above formula, in which Rrepresents a hydrogen atom. In this case, monoazo dyestuffs can beisolated which contain the diazo component linked to theacetoacetylamino group (enolic side). When using diazo components havinga higher coupling energy, such as aniline-sulfonic acids ornitroanilines, monoazo dyestuffs can only be prepared if the naphtholichydroxyl group is previously protected by acylation, for instance withp-toluene-sulfochloride, and resaponified after the coupling. By furthercoupling with another diazotized amine, advantageously in a neutral orweakly alkaline medium, it is possible to prepare disazo dyestuffshaving different diazo components.

As far as the dyestuffs contain groups capable of being metallized, forinstance two hydroxy groups or hydroxycarboxy groups in o,o-position toan azo bridge or groups capable of being converted into such groups,said groups can be converted in known manner into metal complexcompounds. As agents yielding metal there may be used copper, nickel,cobalt, chromium, manganese or iron compounds. By metallizing themonoazo dyestuffs, coupling them to form disazo dyestuffs and treatingthem with another agent yielding metal it is also possible to preparediazo dyestuffs containing different complex-bound metals. A secondhydroxy group which is in o-position to an o-hydroxy-azo group can beintroduced also by ox ydative coppering.

The new dyestuffs are suitable for dyeing and printing various fibrousmaterials, such as for example natural or regenerated cellulosicmaterials, wool, silk or polyamide fibers. They can be fixed on thefibrous material at normal temperature or at an elevated temperature inthe presence of agents having an alkaline reaction or yielding alkali inthe heat. The dyestuffs obtained according to the process of the presentinvention are distinguished by a high tinctorial strength, good toexcellent light and wet fastness properties and, in many cases, by agood affinity for the fiber when the dyeing is carried out by theexhaust process.

As compared with known dyestuffs of similar constitu tion, for examplewith those described in German Patent Nos. 870,883, 956,794 and1,077,812, the new dyestuffs are distinguished by considerably betterproperties of wet fastness.

The following examples serve to illustrate the invention but they arenot intended to limit it thereto, the parts being by weight unlessotherwise mentioned and the relationship of parts by weight to parts byvolume being the same as that of the kilogram to the liter.

Example 1 217 parts of 1-amino-Z-hydroxybenzene-S-B-hydroxyethyl-sulfoneare introduced at room temperature while stirring into 570 parts ofconcentrated sulfuric acid and stirred for several hours untilcompletely dissolved. The mixture is then poured onto 1,500 parts of iceand diazotized at 510 C. with a solution of 70 parts of sodium nitritein 110 parts of water. After addition of 1,000 parts of water and 1,500parts of ice the whole is neutralized by gradually adding the totalamount of 1,000 parts of sodium bicarbonate. The temperature is allowedto rise slowly. At 20 C. the formation of foam ceases. 170 parts of thesodium salt of 1-hydroxy-7-acetoacetylamino-naphthalene-3-sulfonic acidare now introduced into the diazotization mixture, the mixture isadjusted to pH 7.5-8.0 by addition of some sodium bicarbonate, heated to30- 35 C. and stirred for several hours until the coupling is complete.The mixture is then adjusted to a weakly acid pH-value by addition of a20% hydrochloric acid, the dyestuff salted out by means of potassiumchloride and isolated by suction filtration.

The dyestuff which is obtained in the form of a dark brown powderdissolves in water with a red brown color. Its solution changes to redviolet upon addition of alkali.

In the form of its free acid the dyestuff corresponds to the followingformula 180 parts of the dyestuff which is obtained in a concentrationof about 50% are introduced into a solution of 50 parts of crystallizedcopper sulfate and 110 parts of crystallized sodium acetate in 2,000parts of water and the whole is heated for 1-2 hours to C. Afterfiltration of the solution the dyestuff is separated by addition ofsodium chloride and isolated. It is violet brown powder which dissolvesin water with a red brown color and dyes cellulose fibers in thepresence of agents having an alkaline reaction red brown shades whichare fast to washing and to light. The dyestuff contains 2 copper atomsper molecule.

When using for the metallization, instead of the amount of coppersulfate given above, 30 parts of crystallized cobalt sulfate, a dyestuffis obtained in the form of a blackish brown powder which dissolves inwater with a brown color. Prints and padded dyeings prepared with thisdyestuff on cotton fabrics show a strong neutral brown having excellentfastness properties to wetting and to light. Valuable brown dyeings andprints are also obtained on polyaniide fibers.

Example 2 189 parts of 1-amino-2-hydroxybenzene-S-sulfonic acid areintroduced into 3,800 parts of water and 300 parts of concentratedsulfuric acid, and the whole is then diazotized at 5 10 C. with asolution of 70 parts of sodium nitrite in parts of water. The excessivesodium nitrite is decomposed by addition of some amidosulfonic acid. 345parts of the sodium salt of1-hydr0xy-5-acetoacetylamino-naphthalene-3-sulfonic acid are introducedinto the mixture obtained in this manner, the pH-value of the mixture isadjusted to about 4.5 by addition of sodium bicarbonate, then 50 partsof crystallized sodium acetate are added and the whole is stirred atroom temperature until the coupling is complete. The yellow monoazodyestuff separated which corresponds to the formula l so H HO N a isfiltered with suction and subsequently introduced with stirring into2,000 parts of water. Then 310 parts of the inner sulfate of1-diazo-2-hydroxybenzene-S-p-hydroxyethylsulfonyl-sulfuric acid esterare added, the pH-value is adjusted to 7.58.0 by addition of sodiumbicarbonate, the whole is heated to 3540 C. and stirred for severalhours until the coupling is complete. The dyestuff is precipitated byaddition of sodium chloride and then filtered with suction. Itconstitutes a dark brown powder which dissolves in water with a redbrown color. The dyestuff corresponds to the following formula Thecopper complex dyestuif prepared from the dyestuif obtained in themanner described in Example 1 contains 2 copper atoms per molecule. Itconstitutes a red brown powder and dissolves in water with a red browncolor. With this dyestuif strong red brown dyeings having a good wetfastness and a very good fastness to light are obtained on cellulosefibers in a long bath in the presence of alkalies.

The cobalt complex dyestuff prepared in analogous manner contains onlyone cobalt atom per molecule and produces prints and padded dyeingshaving a neutral brown color which is fast to washing and to light.

Example 3 345 parts of the sodium salt of1-hydroxy-7-acetoacetylaminonaphthalene-3-sulfonic acid are dissolved in2,500 parts of water. 308 parts of the inner sulfate of 1-diazo-2-hydroxybenzene-S 8 hydroxyethylsulfonyl-sulfuric acid ester are thenintroduced into this solution While stirring, a 20% sodium acetatesolution is dropped in until the mixture shows a pH-value of 3.0, 500parts of potassium chloride are added and the whole is stirred at about30 C. until the coupling is complete. The monoazo dyestuflf of theformula I i HON l separates gradually from the solution in the form of ayellow precipitate and is isolated by suction.

25 parts of 1-amino-2-methoxy-4-nitrobenzene-S-sulionic acid arediazotized at 10 C. in a solution of 250 parts of water and 25 parts ofconcentrated hydrochloric acid by dropwise addition of 17.5 parts of a40% sodium nitrite solution. The mixture is introduced into a solutionof 63 parts of the above monoazo dyestutf in 250 parts of water and 75parts of anhydrous sodium acetate, and the whole is stirred at roomtemperature until the coupling is complete. The disazo dyestulf formedwhich corresponds to the formula is precipitated by addition ofpotassium chloride. It constitutes a dark brown powder which dissolveswith a red color in water.

parts of the dyestuff which is obtained in a concentration of about 50%are introduced into a solution of 25 parts of crystallized coppersulfate and 55 parts of crystallized sodium acetate in 1,000 parts ofwater and the whole is heated for 2 hours to 80 C. The dyestuff is thenprecipitated by means of potassium chloride and filtered with suction.It contains 1 copper atom per molecule and constitutes a dark brownpowder which dissolves in water with a red brown color. When applied tocotton or polyamide fabrics in the presence of agents having an alkalinereaction the dyestutf obtained produces brown prints having a goodfastness to wetting and to light.

Example 4 159 parts of 1-hydroxy-8-aminonaphthalene 3,6 disulfonic acidare neutralized in 1,300 parts of water, while stirring, by addition ofanyhdrous sodium carbonate, and completely dissolved. 45 parts ofdiketene are then dropped in slowly at room temperature and the whole isstirred for some time until no free amino group can be detected anylonger.

183 parts of 1-aminobenzene-4-vinylsulfone are diazotized in a solutionof 1,000 parts Water and 500 parts by volume of 5 N-hydrochloric acid at5-10" C. by dropwise addition of parts of a 40% sodium nitrite solution.The diazotization mixture is added to the solution ofl-hydroxy-S-acetoacetylaminonaphthalene-3,6-disulfonic acid prepared inthe manner described above. Sodium bicarbonate is slowly introduced,with stirring until a pH-value of 6.5-7.0 is obtained, and the whole isstirred until the coupling is complete. The disazo dyestuif formed issalted out with potassium chloride and filtered with suction. Itconstitutes a dark red powder, dissolves in water with a red color andcorresponds to the following formula When applied to cellulose orpolyamide fibers or wool in the presence of agents having an alkalinereaction the dyestuff yields dark red dyeings or prints having excellentwet fastness properties and a medium fastness to light.

Example 5 217 parts of a1-amino-2-hydroxybenzene-S-B-hydroxyethylsulfone are converted into thesulfuric acid ester in the manner described in Example 1 and diazotized.A solution of l-hydroxy 8 acetoacetylaminonaphthalene- 3,6-disulfonicacid prepared as described in Example 4 is added to the neutralizeddiazotization mixture. The pH- value of the mixture is adjusted to7.5-8.0 by addition of sodium bicarbonate and maintained at this value.The mixture is heated to 3035 C. and stirred until the coupling iscomplete. The dyestufl? is precipitated by acidification withhydrochloric acid and addition of potassium chloride and isolated. Itconstitutes a dark powder and dissolves in water with a yellow redcolor. The color of the solution changes to red violet upon addition ofalkali. The dyestulf corresponds to the following formula 170 parts ofthe dyestuif which is obtained in a concentration of about 60% andheated to the boil within 3 hours in 750 parts of water containing 26parts of chromium triacetate. The reaction mixture is then evaporated todryness in vacuo. The dyestuff which is obtained in the form of a blackpowder dissolves in water with a greyish-green color. The printsobtained on cotton or staple fiber fabrics have a strong olive greencolor of excellent fastness properties to Wetting and light.

Example 6 170 parts of the sodium salt ofl-hydroxy-7acetoacetylamino-naphthalene-3-sulfonic acid are dissolved in2,000 parts of water and 230 parts of the diazoxide of l-amino-2-hydroxy-benzene-5-fi-hydroxyethylsulfone are added with stirring. ThepH-value of the mixture is adjusted to 12.0 by dropwise addition ofsodium hydroxide solution of 380 B. and the whole is stirred for severalhours at room temperature until the coupling is complete. By dropwiseaddition of a hydrochloric acid the mixture is then adjusted so as toshow a weakly acid reaction to Congo paper and stirred until thinlyliquid. The product is then filtered with suction, washed with a smallamount of dilute hydrochloric acid and dried. In its present form thedyestutf is only sparingly soluble in water, but dissolves with a redbrown color upon addition of alkali. It corresponds to the followingformula SO2-CHz-CHz-OH 200 parts of said dyestuff are introduced slowlyand with stirring into 1,000 parts of concentrated sulfuric acid. Thewhole is stirred for several hours at 30 C. until the dyestutf hascompletely dissolved. The mixture is then poured on 3,000 parts of icewhile stirring is continued and the dyestufi is salted out by additionof 800 parts of sodium chloride. After filtration by suction the filtercake which still shows a strongly acid reaction is once more suspendedwith saturated sodium chloride solution, neutralized by careful additionof sodium bicarbonate and again filtered with suction.

The dyestuff which is obtained in the form of a dark brown powder isidentical with that described in Example l and may likewise be convertedinto metal complex compounds.

Example 7 345 parts of the sodium salt ofl-hydroxy-7-acetoacetylamino-naphthalene-3-sulfonic acid are dissolvedin 4,000

parts of water, and 30 parts of glacial acetic acid are added.Subsequently 228 parts of the diazoxide of 1-amino-Z-hydroxy-benzene-S-fi-hydroxyethylsulfone are introduced withstirring, and the whole is stirred for several hours at room temperatureuntil the coupling is complete. The monoazo dyestuff which is obtainedin the form of a yellow precipitate is filtered with suction, washedwith a 5% sodium chloride solution and dried. It corresponds to thefollowing formula parts of the dyestulf which is obtained in aconcentration of about 70% are introduced into 300 parts of anhydrouspyridine and, after addition of 5 parts of urea, heated to C. At thistemperature 35 parts of amidosulfonic acid are gradually introduced andthe whole is then heated for about 1 hour to -105 C. After cooling themixture is poured into 2,500 parts of water, a 20% hydrochloric acid isadded until the mixture shows a weakly acid reaction to Congo paper, theprecipitation of the dyestufl? is completed by introduction of 200 partsof sodium chloride and the dyestutf is filtered with suction.

The sulfuric acid ester of the monoazo dyestuff which is obtained in theform of a yellow powder is identical with the monoazo dyestuff describedin Example 3. By further coupling with any diazotized aromatic aminesdesired disazo dyestuffs can be prepared in the manner described inExample 3.

The esterification in pyridine may be effected in analogous manner withthe aid of chlorosulfonic acid at a temperature between 30 and 40 C.

Example 8 100 parts of the monoazo dyestuff described in Example 3 whichis obtained in a concentration of about 60%, are introduced into asolution of 25 parts of crystallized copper sulfate and 55 parts ofcrystallized sodium acetate in 800 parts of water and stirred for 1 hourat 80 C. After cooling the copper complex dyestuff formed is salted outby means of potassium chloride, filtered with suction and washed withsaturated potassium chloride solution. The moist dyestnff paste is thenintroduced into 500 parts of water, and 31 parts of the inner sulfate of1 amino-Z-hydroxybenzene-5-5-hydroxyethylsulfonyl-sulfuric acid esterare added. The pH-value of the mixture is adjusted to 7.5-8.0 byaddition of some sodium bicarbonate and the Whole is stirred at 35 C.until the coupling is complete. The dyestutf which has been precipitatedwith potassium chloride and isolated is obtained. in the form of a darkbrown powder. It dissolves in water with a red brown color andcorresponds to the following formula 100 parts of said dyestuff which isobtained in a strength of about 50% are stirred up for 1 hour at 80 C.in 500 parts of water containing parts of cobalt acetate. After coolingthe dyestufl is precipitated with potassium chloride and filtered withsuction. The dyestulf which is obtained in the form of a dark brownpowder dissolves in water with a red brown color and, when appliedtocotton or staple fiber fabrics, produces strong brown prints ordyeings showing excellent fastness properties to light and wetprocessing. 2 dyestufi molecules contain together 2 copper atoms and 1cobalt atom.

Example 9 320 parts of 1-hydroxy-7-acetoacetylamino-naphthalene-3-sulfonic acid are dissolved in 3,000 parts of water.

While stirring 644 parts of the inner sulfate of 1-diazo-2-SOz-CHz-CH2OSOH 160 parts of the dyestuff which is obtained in astrength of about 60% are heated to the boil for about hours, in 1,000parts of water containing 60 parts of crystallized copper sulfate, 70parts of crystallized sodium acetate and parts of glacial acetic acid.After cooling the dyestufi is salted out by means of potassium chlorideand filtered with suction. The dyestuif obtained contains 2 copper atomsper molecule and has the same properties and composition as the coppercomplex dyestuff described in Example 1.

Example 10 189 parts of 1 amino 2 hydroxybenzene 5 sulfonic acid areintroduced into a solution of 3,800 parts of water and 300 parts ofconcentrated hydrochloric acid and diazotized at 5l0 C. with 175 partsof a sodium nitrite solution. 345 parts of the sodium salt of 1 hydroxy7 acetoacetylamino-naphthalene 3 sulfonic acid are introduced into thismixture, the pH-value is adjusted to 4.5 by addition of sodiumbicarbonate, parts of crystallized sodium acetate are added 'and thewhole is stirred at room temperature until the coupling is complete. Theyellow monoazo dyestufi precipitates during the operation. 295 parts ofthe inner salt of 1- diazobenzene 4 B hydroxyethylsulfonyl sulfonic acidester are then added, the pH-value is adjusted to 6.06.5 by addition ofsodium bicarbonate and the whole is stirred at room temperature untilthe coupling is complete. The mixture is then adjusted with hydrochloricacid to a pH-value in a weakly acid range, the disazo dyestulf isprecipitated by addition of potassium chloride and filtered withsuction. The dyestuff which is obtained in the form of a red brownpowder dissolves in water .with a red brown color and dyes cotton orangebrown shades. It corresponds to the following formula 135 parts of saiddyestulf which is obtained in a strength of about 60% are introducedinto a solution of 56 parts of crystallized copper sulfate and 60 partsof crystallized sodium acetate in 1,000 parts of water. The pH-value ofthe mixture is adjusted to 5.5-6.0 by addition of a small amount ofanhydrous sodium carbonate. 50 parts of a 15% hydrogen peroxide aredropped into this solution within 2 hours at 1520 C., and the whole isstirred for some time at room temperature. The dyestuff which has beenprecipitated by means of potassium chloride and isolated constitutes abrown powder which dissolves in water with a red brown color. Thedyestuif corresponds to the following formula In the presence of agentshaving an alkaline reaction red brown dyeings and prints of goodfastness properties to light and wetting are obtained on cotton andstaple fibers.

Example 11 520 parts of the sodium salt of 1 (p toluene-sulfonyloxy) 7acetoacetylamino naphthalene 3 sulfonic acid are suspended in 2,500parts of Water. 230 parts of the inner sulfate of 1 diazo 2nitrobenzene- 4-sulfonic acid are introduced while stirring, parts ofanhydrous sodium acetate are added and the whole is stirred until thecoupling is complete. By addition of a small amount of sodium chloridethe monoazo dyestufi precipitates from the solution which has an intenseyellow. color in the form of lemon yellow flakes. The dyestuif isseparated from excessive diazonium salt by suction, the moist filtercake is dissolved in 5,000 parts of water, 1,000 parts by volume ofsodium hydroxide solution of 38 B. are added and the whole is heated fora r 11 short period of time to 90 C. After cooling the whole isneutralized by means of concentrated hydrochloric acid, 310 parts of theinner sulfate of l diazo 2 hydroxybenzene 5 B hydroxyethylsulfonylsulfuric acid esterare added while stirring, the pH-value of the mixtureis adjusted to 7.5-8.0 by addition of sodium bicarbonate and the wholeis stirred at 30-35 C. until the coupling is complete.

The disazo dyestutf formed is precipitated with potassium chloride andfiltered with suction. It constitutes a dark brown powder whichdissolves in water with a red browncolor. The dyestuff corresponds tothe following formula OaN [I OH HO N l 170 parts of the dyestuff whichis obtained in a concentration of about 50% are introduced into asolution of 25 parts of crystallized copper sulfate and 55 parts ofcrystallized sodium acetate in 1,000 parts of water and the whole isheated for 1 hour to 80 C. The dyestuft is precipitated by means ofsodium chloride and filtered with suction. It constitutes a dark brownpowder which dissolves in water with a red brown color. With the use ofthis dyestulr claret dyeings and prints having a good fastness to lightand to wet processing are obtained on cellulose fibers.

Example 12 312 parts of1-amino-2-hydroxy-5-(N-ethionyl-N-methylamino)-benzene are diazotized at5l0 C. in a solution of 2,000 parts of water and 250 parts ofconcentrated hydrochloric acid by dropwise addition of a solution of 70parts of sodium nitrite in 110 parts of water. Excessive sodium nitriteis decomposed by addition of a small amount of urea. 170 parts of thesodium salt of l-hydroxy- 7-acetoacetylamino-naphthalene-3-sulfonic acidare then introduced into the mixture, the pH-value is adjusted to 7.5 byaddition of sodium bicarbonate and the whole is stirred for severalhours at room temperature until the coupling is complete. The dyestutfwhich has been precipi tated by addition of potassium chloride andisolated constitutes a dark brown powder which dissolves in water with abrown color. In the form of its free acid it corresponds to thefollowing formula The copper complex dyestutf prepared from the abovedyestufl in the manner described in Example 1 contains 2 copper atomsper molecule. The dyestulf constitutes a brown powder which dissolves inwater with a red brown color. When applied to cotton .or staple fibersin the presence of agents having an alkaline reaction the dyestuffyields red brown dyeings and prints having an excellent fastness tolight and washing.

The corresponding cobalt complex dyestufr' contains only 1 cobalt atomper molecule and yields neutral brown prints.

Example 13 170 parts of the sodium salt ofl-hydroxy-S-acetoacetylamino-naphthalene-3-sulfonic acid are dissolvedin 1,700 parts of water. 295 parts of the inner sulfate of 4 ([3chloropropionylamino)-l-diazobenzene-2-sulfonic acid are introducedwhile stirring, the pH-value of the mixture is adjusted to the point ofneutrality by addition of some sodium bicarbonate and the whole isstirred until the coupling is complete. The dyestutf which hasprecipitated in the form of crystals is filtered with suction. It

constitutes a dark red powder and corresponds to the following formulaThe dystuff dissolves in water with a yellowish-red color. On cellulosefabrics it produces red prints and padded dyeings having excellentproperties of wet fastness.

Example 14 63 parts of the monoazo dyestuff obtained as described inExample 3 are introduced into 600 parts of water, and 26 parts of theinner sulfonate of 5-acroy1amino-1-diazobenzene-Z-sulfonic acid areadded while stirring. The pH- value of the mixture is maintained at7.07.5 by addition of some sodium bicarbonate, and the whole is stirredfor several hours until the coupling is complete.

The dyestuff is precipitated with potassium chloride and filtered withsuction. It is obtained in the form of a dark brown powder, whichdissolves in water with a yellowishbrown color. The dyestuff correspondsto the following formula H SOaH HO N 177 parts of the dyestuff which isobtained in a concentration of about 50% are introduced into a solutionof 25 parts of crystallized copper sulfate and 55 parts of crystallizedsodium acetate in 1,500 parts of water and the Whole is heated for 1-2hours to 80 C. After cooling the dyestuff is salted out by addition ofsodium chloride.

water with a yellowish-brown color. The dyestuff contains 1 copper atomper molecule. On cotton and polyamide fibers the dyestuff yields clearbrown shades having a good fastness to light and to washing.

Example 15 170 parts of the metal-free dyestulf prepared as described inExample 5 and having a purity of about 60% are dissolved in 900 parts ofwater. Within 1 hour 60 parts of sodium hydroxide solution of 38 B aredropped in at room temperature while stirring and stirring is continuedfor some time. The mixture is then neutralized by dropwise addition of a20% hydrochloric acid, the vinylsulfone dyestuff formed is salted out byaddition of 100 parts of sodium chloride and isolated by suctionfiltration. The dyestuff constitutes a dark brown powder and dissolvesin water with the same color as the starting dyestulf but is moresparingly soluble than the latter. The dyestufi corresponds to thefollowing formula 135 parts of the dyestuff which is obtained in astrength of about 60% are heated for about 1 hour to 80 C. in 750 partsof water containing 15 parts of cobalt acetate. After cooling 250 partsof sodium chloride are added, thus causing the precipitation of adyestufi containing only 1 cobalt atom per 2 dyestufi molecules. Thedyestuff which is obtained in the form of a blackish brown powderdissolves in water with a dark red brown color. The prints obtained oncotton or staple fiber fabrics show a strong dark brown shade having anexcellent fastness to light and to washing.

Example 16 189 parts of 1-amino-2-hydroxybenzene-S-sulfonic acid arediazotized in the manner described in Example 2. 345 parts of the sodiumsalt of l-hydroxy-7-acetoacetylaminonaphthalene-3-sulfonic acid areintroduced into the mixture obtained in this manner, the pH-value isadjusted to 4.0 by addition of sodium bicarbonate, 100 parts ofcrystallized sodium acetate are added and the whole is stirred forseveral hours until the coupling is complete. In the course of thisoperation the yellow monoazo dyestuff formed precipitates partially.Then 230 parts of the diazoxide of1-amino-2-hydroxybenzene-S-B-hydroxyethylsulfone are added, the pH-valueof the mixture is adjusted to 9.0-9.5 by addition of anhydrous sodiumcarbonate and the whole is stirred for several hours at room temperatureuntil the second coupling is complete. The mixture is then adjusted to apH-value in a weakly acid range by dropwise addition of a 20%hydrochloric acid, and the precipitation of the disazo dyestuff iscompleted by addition of sodium chloride. The dyestulf which is obtainedin the form of a dark red powder dissolves in water with a red color,and upon addition of alkali the solution changes to dark red witha'greyish-green dichroism. The dyestutf corresponds to the followingformula 125 parts of said dyestulf which is obtained in a concentrationof about 60% are slowly introduced into 625 parts of concentratedsulfuric acid while stirring. Stirring is continued for several hours atroom temperature until the dyestulf has completely dissolved.Subsequently, the mixture is poured onto 1,900 parts of ice whilestirring, the esterified dyestuff is salted out by addition of sodiumchloride, filtered with suction and washed with saturated sodiumchloride solution. The moist filter cake is then dissolved in 1,000parts of water and neutralized with some sodium hydroxide solution.Within about 30 minutes 50 parts of a 36% potassium hydroxide solutionare dropped in at room temperature and the whole is stirred parts of thedyestuff which is obtained in a concentration of about 60% are convertedinto the cobalt complex in the manner described in Example 15. Duringthe operation a dyestulf precipitates which contains 1 co balt atom per2 dyestuif molecules. The dyestufi is obtained in the form of a blackishbrown powder and dissolves in water with a brown color. The prints andpadded dyeings obtained on cotton or staple fiber fabric show a neutralbrown color of an excellent fastness to light and to washing.

The corresponding chromium complex dyestutf containing l chromium atomper dyestulf molecule yields blackish-brown shades having likewiseexcellent fastness properties.

The dyestuffs specified in the following table can be prepared inanalogous manner. They also yield dyeings and prints of good fastnessproperties.

Diazo components Coupling component Metal Tint I. Enolic side II.Naphtholic side l-amino-2-hydroxybenzene-5-fl-hydroxy-1-amino-2-hydroxybenzene-Hi-hydroxyl-hydroxy-7-acetoacetylaminonaph- CrBlackishethylsulionylsulfuric acid ester. thalene-B-suiionic acid.brown.

0 dn Ni Red brown. l-amino-2-hydroxybenzene-5-sulfonic acid Do. Neutralbrown. 1-amino-2-hydroxy-3-chlorobenzene-5- -do do Go Do.

sulfonic acid. l-amino-2-hydroxybenze11e-5sulionic acid.l-amino-benzene-4-B-hydroxyethyl- -..do Cu Clear redsulfonyl-sulfuricacid ester. V brown. Do do do Co Yellowish brown. Dol-aminobenzene-3-B-chloroethylsulfone do Cu Red brown.1-amino-2-hydroxybenzene-S-B-hydroxyl-aminobenzeue-i-sulfonic acid -doCu Do ethyisulfonylsuliuric acid ester.

Do do ..do 00 Brown. Do l-an 31o-2-hydroxybenzene-5-sulionic .do Cu Redbrown.

aci Do do dn Co Neutral brown. Do l-aminonaphthaleue-4-sulfonic acid .doCu Red brown.1-amin0-2-hydroxybenzenei-fl-hydroxyl-amino-2-hydroxybenzene-M9-hydr0xy--do Cu Do ethylsuhonylsulfurie acid ester. ethylsulionyisuliuric acidester;

Do do .do Co Neutral brown. Do d Cr Blackish brown.l-amino-2-hydr0xybenzene-5-sulfonic acid dn Cu Violet-tinged rown. Do dodo Co Greyish brown. Do do -.do Or Blackish brown. laminobenzene-d-B-hydroxyethylsull-amino-benzene-4-5-hydroxyethylsuldoClaret.

fonylsulfuric acid ester. fouylsuliuric acid ester.l-amino-2-hydroxybenzene-fi-fi-hydroxyl-aminobenzene-2-carboxylicacid-4.- .do Cu Red brown.

ethylsulfonylsuliuric acid ester. sulfonic acid.

Do- .do ..do Co Yellowish brown. Do Or Neutral brown.1-aminobenzene-2-carboxylic acid-5- 1-aminobenzene-2-carboxylicacid-E-fl- -do Cu Red brown.

hydroxyethylsulionyl-suliuric acid hydroxyethylsulionyl-suliuric acidester. ester.

Do d 00 Brown. Do .d0 Red brown. l-amino-z-nitrobenzene-sulionicacid..... 1-aminobenzene--fl-hydroxyethylsul- Do.

fonyl-sulfuric acid ester. D0 1-amino-2-hydroxybenzene-S-fl-hydroxy- .doCu Claret.

ethylsulfonyl-suliuric acid ester. D do -do Co Violetish red brown.l-aminobenzene-Z-carboxylic acid -do 1-hydroxy-B-acetoacetylamino-uaph-Cu Red brown.

thalene-B-sulfonic acid. Do. Brown. Claret. Reddish brown.l-hydroxy-5-acetoacety1amino-naph- Cu Red brown.

thalene-3-sulfonic acid. Co Neutral brown. Yellowish ionyl-suliuric acidester. brown. o Brown. Do l-aminobenzene-ifl-hydroxyethylsul- Dionyl-phosphoric acid ester. l-aminobenzene-3-fl-hydroxyethyisul-1-aminobenzene-3-B-hydroxyethylsul- Scarlet.

fonyi-sulfuric acid ester. fonyl-sulfuric acid ester.1-amino-2-hydroxybenzene-fi-B-hydroxy-1-amino-2-hydroxybenzene-fi-B-hydroxy-1-hydroxy-7-(acetoacetyl-N-methyl- Cu Red brown.

ethylsulionyl-suifuric acid ester. ethylsulionyl-sulfuric acid ester.amino)-naphtha1ene-3-sulionic acid.

Dn do 7 Co Reddish dark brown. do Cr Bluish brown.1-hydroxy-7-acetoacetylamino-nap h- Cu Red brown.

thalene-3,6-disulfonic acid.

do Co Neutral brown. Dn rin do Gr Greyish brown. D dn 1hydroxy-S-acetoacetylamino-naph- Cu Violet-tinged thalene-5-suliom'cacid. dark brown.

Do Do.l-amino-2-hydroxybenzene-S-B-hydroxyl-amino-2-hydroxybenzene-5-B-hhydroxy toacetylamino-naph- Cu D0.

ethylsulionyl-suliuric acid ester. ethylsulfonyl-suliuric acid ester.tha1eue-3,6-disu1ionic acid.

Dn fin an Co Blackish brown. 3,, (in (in Ruby red. Do "d do Claret. Dn d.do-..- Yellowish brown. l-amino-2-hydroxynaphthalene-4-suldoViolet-tinged fonic acid. rown.

Do do Violetish red brown. Do do ..d0 Cr Grey.l-amino-2-hydr0Xy-3-nitrobenzene-5-B-l-amino-2-hydroxy-3-nitrobenzene-5-fi- ...do Cu Violetish red hzdroxyethylsulicnyl-suliuric acid h adroxyethylsulionyl-sulfuric acidbrown. es er. es er.

Do do .J Co Violet-tinged grey.l-aminobenzene-iifl-hydroxyethylsull-amincbenzene-3-fl-hydroxyethylsulnScarlet.

i'onylphosphoric acid ester. fonyl-phosphoric acid ester.1-aminobenzene-3-fl-chloroethyisulfone1-aminobenzene-3-B-chloroethylsuli'one .do Do.l-amino-2,5-dimethoxybenzene-ivinyl-1-amino-2,5-dimethoxybenzene-4-vinyl- -do Ruby red.

sulioue. fone.

Diazo components Coupling component Metal Tint I: Enolic side 11.Naphtholic sideI-amino-Z-hydroxybenzene-B-B-hydroxyl-amino-Z-hydroxybenzene--fl-hydroxyl-hydroxy-8-acetoacetylamino-naph-On Bed brown.

ethylsulionyl-sulfuric acid ester. ethylsulfonyl-suliuric acid ester.tha1ene-3,5-disu1fonic acid.

D do do 00 Dark brown. D do..-...- .d0 Or Greyish brown. D1-hydroxy-3-aeetoacetylaminobenzene-i- Cu Red brown.

sulfonic acid. Do do ..d0 Go Do; l-amino-2-hydroxybenzene-5-su1fonicacid. 1-arnino-4-(N-methyl-N-ethionyl)-1-hydroxy-7-acetoacetylamino-naph- Cu Do.

aminobenzene. thalene-3-sulfonie acid. Do ..do Cr Turbid red. Do.-.l-amino-de(N-methyl-N-vinylsuifonyh- Red brown.

aminobenzene. Do 1-amino-4-acroy1aminobenzene do Cu Do. Do do (in Do, Dol-amino-2-methoxy-x-B-chloropropionyl- .do Do.

benzene (obtained by reaction of 1- arnino-Z-methoxybenzene with B-ohloropropionylchloride according to Friedel-Craits).1-amino-2hydroxybenzene-5-fl-hydroxy- 1-amino-4-B-hydroxyproplonylamino-'-....do Cu Do.

ethylsuiionylsuliuric acid ester. benzene-sulfuric acid ester.1-amino-4-(N-methyl-N-fi-ch1oroethyll-amino14-(N-methyl-N-fl-chloroethyll-hydroxy-S-acetoacetylamiuo-naph-Dark red.

sulfonyD-aminobenzene. sulfonyl)-aminobenzene. tha1ene-3,6-disuiionicacid.

We claim: 2. The complex chromium compound of the dyestuff 1.Water-soluble dlSaZO dyestufi of the formula of the formulaSOz-CHz-CHz-O-SOaH R;Ar1 N XZ I H OH OH L so Ho N i N 11-1 1 I i ll o=C-CO-NH N=N HO N OH R: H3C=-C ONAI1N=NA.I3E N X-Z SOgH L k (S z )n n-lw-r SO:CHz-CH2O- Oa 3. The compleir copper compound of the dyestutf ofthe formula SO3H or a complex metal compound thereof containing a metal40 R of the group consisting of copper, cobalt, nickel, chro- 110- mium,manganese and iron, wherein Ar represents a member selected from thegroup consisting of benzene N and naphthalene; Ar and Ar representmembers selected H0 'l SOZH from the group consisting of benzene,naphthalene, benzene sulfonic acid, naphthalene sulfonic acid, loweralk- EXPO-C43 0-NH SOF'CHT'CHPO BOQH oxy-benzenes, nitrobenzenes,nitrobenzene sulfonic acid, 4. The complex chromium compound of thedyestufi of lower alkoxy-nitrobenzene sulfonic acid and chlorobentheformula zene sulfonic acid radicals, R represents a member selected fromthe group consisting of hydrogen and lower alkyl, R represents a memberselected from the group consisting of hydrogen and lower alkyl, Rrepresents a member selected from the group consisting of hydrogen,hydroxyl, carboxyl and lower alkoxy; X represents a member selected fromthe group consisting of sultonyl H0 1i SOr-CHz-CHr-O-SOaH and carbonyl,Z represents a member selected from the L NH 0H OH group consisting of13-chloroethyl, B-sulfatoethyl, fi-phos- I phatoethyl and vinyl, 1:stands for one of the integers 1 and 2, m and m stand for one of theintegers 1 and 2 the sum of mand m being at least 3, and p stands forE03 S03]; one of the integers 1 and 2, and wherein the groups R in Arand Ar and -OH in Ar; are each linked in orthoposition to the adjacentazo group. 5. The dyestufi of the formula SOBH 0 l l -l| A) N 0 Cu--0 li Haoi:=o-co-NH N= =N SOaH -S0:CH:CH2

6. The complex copper compound of the dycstuff of the formula 7. Thecomplex cobalt compound of the dyestulf of 20 the formula I SOaGH=CH:

I HO

1103s son;

References Cited UNITED STATES PATENTS FLOYD D. HIGEL, Primary Examiner.

US. Cl. X.R.

